Evaluation of the Impact of Ruminant Trans Fatty Acids on Human Health: Important Aspects to Consider

The definition and evaluation of trans fatty acids (TFA) with regard to foodstuffs and health hazard are not consistent. Based on the current situation, the term should be restricted only to TFA with isolated double bonds in trans-configuration. Conjugated linoleic acids (CLA) should be separately assessed. Ideally, the origin of the consumed fat should be declared, i.e., ruminant TFA (R-TFA) and industrial TFA (non-ruminant; I-TFA). In ruminant fat, more than 50% of R-TFA consists of vaccenic acid (C18:1 t11). In addition, natural CLA, i.e., c9,t11 CLA is also present. Both are elevated in products from organic farming. In contrast to elaidic acid (t9) and t10, which occur mainly in partially hydrogenated industrial fat, t11 is partially metabolized into c9,t11 CLA via Δ9-desaturation. This is the major metabolic criterion used to differentiate between t11 and other trans C18:1. t11 indicates health beneficial effects in several studies. Moreover, CLA in milk fat is associated with the prevention of allergy and asthma. An analysis of the few studies relating to R-TFA alone makes clear that no convincing adverse physiological effect can be attributed to R-TFA. Only extremely high R-TFA intakes cause negative change in blood lipids. In conclusion, in most European countries, the intake of R-TFA is assessed as being low to moderate. Restriction of R-TFA would unjustifiably represent a disadvantage for organic farming of milk.     

Heterogeneous Enantioselective Hydrogenation of Activated Ketones Catalyzed by Modified Pt‐Catalysts: A Systematic Structure‐Selectivity Study

A systematic structure‐selectivity study was carried out for the enantioselective hydrogenation of activated ketones with chirally modified Pt/Al₂O₃ catalysts. For this, 18 modifiers containing an extended aromatic system able to form a strong adsorption complex with the Pt surface, and a suitable chiral group with an amino function capable to interact with the keto group of the substrate ( HCd, Qd, HCn, Qn , and semi‐synthetic derivatives, as well as synthetic analogues) were prepared and tested on 8 different activated ketones in AcOH and toluene under standard conditions. It was found that relatively small structural changes of the substrate and/or modifier structures strongly affected the enantioselectivity, and that no “best” modifier exists for all substrates. The highest ees for all substrates were obtained with quinuclidine‐derived modifiers in combination with naphthalene or quinoline rings, either in AcOH (substrates 1 – 5 and 8 , all carrying an sp³ carbon next to the keto group) or toluene ( 6 and 7 , with an sp² carbon next to the ketone). The presence and nature of the substituent R' at the quinuclidine significantly affected the ee (positive and negative effects). Certain combinations of an aromatic system and an amino function were preferred: For the quinuclidine moiety, quinoline and to a somewhat lesser extent naphthalene were a better match, while for the pyrrolidinylmethyl group anthracene was better suited. Methylation of the OH group often had a positive effect for hydrogenations in AcOH but not in toluene. With the exception of 8 , higher ees were obtained for the Cd / Qn series [leading to (R)‐products] than for the Cn / Qd series [leading to (S)‐products]. In several cases, opposite structure‐selectivity trends were detected when comparing reactions in toluene and AcOH, indicating a significant influence of the solvent.     

The Use of Pro-Angiogenic and/or Pro-Hypoxic miRNAs as Tools to Monitor Patients with Diffuse Gliomas

IDH (isocitrate dehydrogenase) mutation, hypoxia, and neo-angiogenesis, three hallmarks of diffuse gliomas, modulate the expression of small non-coding RNAs (miRNA). In this paper, we tested whether pro-angiogenic and/or pro-hypoxic miRNAs could be used to monitor patients with glioma. The miRNAs were extracted from tumoral surgical specimens embedded in the paraffin of 97 patients with diffuse gliomas and, for 7 patients, from a blood sample too. The expression of 10 pro-angiogenic and/or pro-hypoxic miRNAs was assayed by qRT-PCR and normalized to the miRNA expression of non-tumoral brain tissues. We confirmed in vitro that IDH in hypoxia (1% O₂, 24 h) alters pro-angiogenic and/or pro-hypoxic miRNA expression in HBT-14 (U-87 MG) cells. Then, we reported that the expression of these miRNAs is (i) strongly affected in patients with glioma compared to that in a non-tumoral brain; (ii) correlated with the histology/grade of glioma according to the 2016 WHO classification; and (iii) predicts the overall and/or progression-free survival of patients with glioma in univariate but not in a multivariate analysis after adjusting for sex, age at diagnosis, and WHO classification. Finally, the expression of miRNAs was found to be the same between the plasma and glial tumor of the same patient. This study highlights a panel of seven pro-angiogenic and/or pro-hypoxic miRNAs as a potential tool for monitoring patients with glioma.     

Classification of Amyloidosis by Model-Assisted Mass Spectrometry-Based Proteomics

Amyloidosis is a rare disease caused by the misfolding and extracellular aggregation of proteins as insoluble fibrillary deposits localized either in specific organs or systemically throughout the body. The organ targeted and the disease progression and outcome is highly dependent on the specific fibril-forming protein, and its accurate identification is essential to the choice of treatment. Mass spectrometry-based proteomics has become the method of choice for the identification of the amyloidogenic protein. Regrettably, this identification relies on manual and subjective interpretation of mass spectrometry data by an expert, which is undesirable and may bias diagnosis. To circumvent this, we developed a statistical model-assisted method for the unbiased identification of amyloid-containing biopsies and amyloidosis subtyping. Based on data from mass spectrometric analysis of amyloid-containing biopsies and corresponding controls. A Boruta method applied on a random forest classifier was applied to proteomics data obtained from the mass spectrometric analysis of 75 laser dissected Congo Red positive amyloid-containing biopsies and 78 Congo Red negative biopsies to identify novel “amyloid signature” proteins that included clusterin, fibulin-1, vitronectin complement component C9 and also three collagen proteins, as well as the well-known amyloid signature proteins apolipoprotein E, apolipoprotein A4, and serum amyloid P. A SVM learning algorithm were trained on the mass spectrometry data from the analysis of the 75 amyloid-containing biopsies and 78 amyloid-negative control biopsies. The trained algorithm performed superior in the discrimination of amyloid-containing biopsies from controls, with an accuracy of 1.0 when applied to a blinded mass spectrometry validation data set of 103 prospectively collected amyloid-containing biopsies. Moreover, our method successfully classified amyloidosis patients according to the subtype in 102 out of 103 blinded cases. Collectively, our model-assisted approach identified novel amyloid-associated proteins and demonstrated the use of mass spectrometry-based data in clinical diagnostics of disease by the unbiased and reliable model-assisted classification of amyloid deposits and of the specific amyloid subtype.     

Development of dieldrin,endosulfan, and hexachlorobenzene‐imprinted polymers for dye‐displacement array sensing

Due to the toxicity associated with the exposure to organochlorine pesticides, new materials capable of selectively capturing and detecting these compounds are highly desirable. In this study, imprinted polymers were prepared using three organochlorine pesticides—dieldrin (DE), endosulfan (EN), or hexachlorobenzene (HCB) as templates. The MIPs were polymerized via precipitation polymerization. The yields were over 90% with particle sizes ranging from 62 to 214 nm. Binding studies combined with GC‐ECD analysis showed that each template is more selective to its corresponding MIP compared with the other two structurally homologous templates. These results were consistent with those obtained using UV–vis where more bromocresol green (BCG) dye was released when higher template concentrations were introduced to the corresponding BCG‐impregnated MIPs. Since unique selectivity response pattern for each of the MIPs was obtained, this demonstrated that the MIPs were selective and can be potentially used in dye‐displacement array sensing. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44401.     

Photoinitiator-free photopolymerization of acrylate-bismaleimide mixtures and their application for inkjet printing

There is growing interest in using photoinitiator-free systems in coating applications such as inkjet-printing, because residual photoinitiator can alter the properties of the resulting polymer. Bismaleimides (BMI) offer the opportunity to polymerize acrylates without the addition of photoinitiators, as this class of molecules can serve both as polymerizable monomer and as photoinitiator together with electron donor systems, like vinyl ether monomers or acrylates. The UV-induced copolymerization of a low-molecular-weight BMI with various acrylate monomers and oligomers without any photoinitiator was characterized. The BMI-acrylate systems show comparable polymerization speeds to widely used acrylic systems with photoinitiator. Superior thermal stability as well as thermomechanical properties are achieved by enhancing acrylics with BMI. Such photoinitiator-free systems lend themselves to be used for low-migration coatings as well as for high-temperature applications. Here, a characterization of selected BMI-acrylate mixtures regarding their photocuring kinetics and their application as inks for inkjet printing is shown. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47789.     

Eumelanin for nature‐inspired UV‐absorption enhancement of plastics

In the human body, the black‐brown biopigment eumelanin blocks harmful ultraviolet (UV) radiation. In the plastics industry, additives are often added to polymers to increase their UV‐absorption properties. We herein report an assessment of the biopigment eumelanin as a nature‐inspired additive for plastics to enhance their UV absorption. Since eumelanin is produced by natural sources and is nontoxic, it is an interesting candidate in the field of sustainable plastic additives. In this work, the eumelanin‐containing films of commercial ethylene–vinyl acetate copolymer, a plastic used for packaging applications, were obtained by melt compounding and compression molding. The biopigment dispersion in the films was improved by means of the melanin free acid treatment. It was observed that eumelanin amounts as low as 0.8 wt% caused an increase of the UV absorption, up to one order of magnitude in the UVA range. We also evaluated the effect of eumelanin on the thermal stability and photostability of the films: the biopigment proved to be double‐edged, working both as UV‐absorption enhancer and photo‐prooxidant, as thermogravimetric analysis and infrared spectroscopy revealed. © 2019 Society of Chemical Industry